The enantioselective assay for S(+)- and R(-)-propafenone (PPF) in human urine that developed in this work involves extraction of propafenone from human urine and using S(+)-propafenone as internal standard, chiral de...The enantioselective assay for S(+)- and R(-)-propafenone (PPF) in human urine that developed in this work involves extraction of propafenone from human urine and using S(+)-propafenone as internal standard, chiral derivatization with 2,3,4,6-tetra-O-b-D-glucopranosyl isothiocyanate, and quantitation by an RP-HPLC system with UV detection (l=220 nm). A baseline separation of propafenone enantiomers was achieved on a 5-mm reverse phase ODS column, with a mixture of methanol:water:glacial acetic acid (25:12:0.02,v/v) as mobile phase. There was good linear relationship from 24.9 ng/ml to 1875.0 ng/ml for both of enantiomers. The regression equations of the standard curves based on CS-PPF (or CR-PPF ) versus ratio of AS-PPF/AS (or AR-PPF/AS ) were y=0.0032x-0.081, (r=0.999) for S-PPF and y=0.0033x+0.0039, (r=0.998) for R-PPF, respectively. The method抯 limit of detection was 12.5 ng/ml for both enantiomers, and the method抯 limit of quantitation was 28.20.52 ng/ml for S-PPF, 30.40.53 ng/ml for R-PPF (RSD<8%, n=5). The analytical method yielded average recovery of 98.9% and 100.4% for S-PPF and R-PPF, respectively. The relative standard deviation was no more than 6.11% and 6.22% for S-PPF and R-PPF, respectively. The method enabled study of metabolism of S(+)- and R(-)-propafenone in human urine. The results from 7 volunteers administered 150 mg racemic propafenone indicated that propafenone enantiomers undergo stereoselective metabolism and that in the human body, S(+)-propafenone is metabolized more extensively than R(-)- propafenone.展开更多
The different interactions between a chemosensor, 1-（naphthalen-2-yl）-3-（6-nitrobenzothiazol-2-yl）-thiourea （1）, and F, acetate （AcO-）, Cl-, and Br- anions have been investigated theoretically at the B3LYP/6-3...The different interactions between a chemosensor, 1-（naphthalen-2-yl）-3-（6-nitrobenzothiazol-2-yl）-thiourea （1）, and F, acetate （AcO-）, Cl-, and Br- anions have been investigated theoretically at the B3LYP/6-31＋G（d,p） level with the basis set superposition error （BSSE） correction. It was found that the high selectivity of compound 1 for F- can be ascribed to the ability of the anion to deprotonate the N-H fragment of the host sensor, while the chemosensor also has a strong affinity for AcO- by virtue of the formation of a hydrogen-bonded complex. Intramolecular charge transfer （ICT） causes the colorimetric signaling of compound 1 after interaction with F-/AcO. A study of substituent effects suggested that the O/NH- and O/S-substituted derivatives are also expected to be promising candidates for chromogenic F3AcO chemosensors.展开更多
基金Project supported by the National Natural Science Foundation of China (No. 30225047) and by SRF for ROCS+2 种基金 SEM and Zhejiang Provincial Natural Science Foundation (No. RC97016) China
文摘The enantioselective assay for S(+)- and R(-)-propafenone (PPF) in human urine that developed in this work involves extraction of propafenone from human urine and using S(+)-propafenone as internal standard, chiral derivatization with 2,3,4,6-tetra-O-b-D-glucopranosyl isothiocyanate, and quantitation by an RP-HPLC system with UV detection (l=220 nm). A baseline separation of propafenone enantiomers was achieved on a 5-mm reverse phase ODS column, with a mixture of methanol:water:glacial acetic acid (25:12:0.02,v/v) as mobile phase. There was good linear relationship from 24.9 ng/ml to 1875.0 ng/ml for both of enantiomers. The regression equations of the standard curves based on CS-PPF (or CR-PPF ) versus ratio of AS-PPF/AS (or AR-PPF/AS ) were y=0.0032x-0.081, (r=0.999) for S-PPF and y=0.0033x+0.0039, (r=0.998) for R-PPF, respectively. The method抯 limit of detection was 12.5 ng/ml for both enantiomers, and the method抯 limit of quantitation was 28.20.52 ng/ml for S-PPF, 30.40.53 ng/ml for R-PPF (RSD<8%, n=5). The analytical method yielded average recovery of 98.9% and 100.4% for S-PPF and R-PPF, respectively. The relative standard deviation was no more than 6.11% and 6.22% for S-PPF and R-PPF, respectively. The method enabled study of metabolism of S(+)- and R(-)-propafenone in human urine. The results from 7 volunteers administered 150 mg racemic propafenone indicated that propafenone enantiomers undergo stereoselective metabolism and that in the human body, S(+)-propafenone is metabolized more extensively than R(-)- propafenone.
基金supported by the Natural Science Foundation of Inner Mongolia Autonomous Region (2011ZD02)
文摘The different interactions between a chemosensor, 1-（naphthalen-2-yl）-3-（6-nitrobenzothiazol-2-yl）-thiourea （1）, and F, acetate （AcO-）, Cl-, and Br- anions have been investigated theoretically at the B3LYP/6-31＋G（d,p） level with the basis set superposition error （BSSE） correction. It was found that the high selectivity of compound 1 for F- can be ascribed to the ability of the anion to deprotonate the N-H fragment of the host sensor, while the chemosensor also has a strong affinity for AcO- by virtue of the formation of a hydrogen-bonded complex. Intramolecular charge transfer （ICT） causes the colorimetric signaling of compound 1 after interaction with F-/AcO. A study of substituent effects suggested that the O/NH- and O/S-substituted derivatives are also expected to be promising candidates for chromogenic F3AcO chemosensors.
